Hydraulic composition

ABSTRACT

WHEREIN R is a member selected from the group consisting of hydrogen, an alkyl radical of 1-4 carbon atoms and the -COOM group, and M is a member selected from the group consisting of hydrogen, an alkali metal atom, a half atom of an alkaline earth metal and the ammonium group, which M may be the same or different.   A hydraulic composition comprising 100 parts by weight of a hydraulic substance and 0.01 -5 parts by weight of a 3,6endomethylenehexahydro-o-phthalic acid-4-sulfonic acid derivative of the formula

106-97. AU 115 EX 3 1l75 XR 398709533 United States Patent [191 [111 3,870,533

Ogura 1 Mar. 11, 1975 1 HYDRAULIC COMPOSITION [57] ABSTRACT [75] Inventor: Shunichiro Ogura, Tokyo. Japan A hydraulic Composition comprising 100 P y weight of a hydraulic substance and 0.01 -5 parts by [73] Assignee: Nippon Zeon Co., Ltd., Tokyo, weight of u 3.6-endomethylenehexnhydro-o-phthalic Japan acid-4-sulfonic acid derivative of the formula [22] Filed: Nov. 26, 1973 [21] Appl. No.: 419,062

1 R a: :H [30] Foreign Application Priority Data 7 Dec. 8, 1972 Japan 47 1.310 m [52] U.S. Cl. 106/90, 106/97 [51] Int. Cl C04b 7/02 [58] Field of Search 106/90, 97

wherein R 15 a member selected from the group con- [56] References Cited sisting of hydrogen, an alkyl radical of 1-4 carbon UNITED STATES PATENTS atoms and the COOM group, and M is a member selected from the group consisting of hydrogen, an al- 2,3l4,846 3/1943 McClellan C1211. 260/468 metal atom a half mum of an alkaline earth metal 3.145174 3/1964 Pulchen 106/91) g I 3332.777 2/1966 Bush 106/97 and group M be or different.

Primary Examiner-J. Poer 2 Claims, No Drawings Attorney, Agent, or Firm-Sherman & Shalloway HYDRAULIC COMPOSITION This invention relates to a hydraulic composition which can provide mortar or concrete of good workability by the addition of a relatively small amount of water and, in addition, manifests high strength at a relatively early period after the mortar or concrete has set.

As this kind of hydraulic composition, there has been known hitherto that prepared by incorporating in the hydraulic substance an additive such as polyalkylarylsulfonates or lignin sulfonates obtained from the sulfite pulping process, etc. However, these additives were not entirely satisfactory, since they did not manifest any effects when used in small amounts. On the other hand, when they are used in too great an amount, there were such drawbacks as that an excessive amount of air would be entrained, that setting would be retarded, or that drop in the strength of the hardened product would be brought about.

The object of this invention resides in finding a new additive not possessing these drawbacks and thus provide an improved hydraulic composition.

I found that the foregoing object could be achieved by using as the additive 3,6-endomethylene-hexahydroo-phthalic acid-4-sulfonic acid derivatives of the formula R soot m s E coon wherein R is either hydrogen, an alkyl radical of l 4 carbon atoms of the COOM group, and M, which may be the same or different, is either hydrogen, an alkali metal atom, a half atom of an alkaline earth metal or the ammonium group. Hence, in accordance with the present invention, there is provided a novel hydraulic composition which comprises a hydraulic substance incorporated with this type of additive.

It is disclosed in U.S. Pat. No. 2,3 l4,846 that an ester of sulfonated cis-endomethylene-3,6-tetrahydrophthalic acid is used as a detergent. However, there is no suggestion at all therein of 3,6-endomethylene-hexahydro-o-phthalic acid-4-sulfonic acid being effective as an additive to be used with the hydraulic substances.

By the expression hydraulic substance", as herein used, is meant, as usually defined, a substance that has the property of hardening by setting up a hydration reaction when mixed with water. As typical examples, mention can be made of portland cement, alumina cement, blast furnace slag and mixtures of quicklime and siliceous sand.

The 3,6-endomethylenehexahydro-o-phthalic acid- 4-sulfonic acid derivatives of the foregoing generic formula are exemplified by such as 3,6-endomethylenehexahydro-o-phthalic acid-4-sulfonic acid, methyl-3,6- endomethylene-hexahydro-o-phthalic acid-4-sulfonic acid, carboxy-3,fi-endomethylene-hexahydro-ophthalic acid-4-sulfonic acid, and the sodium, potassium. magnesium. calcium and ammonium salts of the foregoing several compounds.

While there is imposed no particular restriction as to the amount these additives are added to the hydraulic substance, conveniently used is 0.01 5 parts by weight, and especially 0.05 1 part by weight, per 100 parts by weight of the hydraulic substance.

The hydraulic composition of the invention obtained by incorporating the aforesaid additives in the hydraulic substance not only excels in its workability when it is to be mixed with water but also excels in its workability when the resulting mortar or concrete is to be used.

Moreover, it can impart great strength to the hardened mortar or concrete at an early period. The mechanism by which these effects are brought about in the invention hydraulic composition is not clear. However, it is presumed that in all probability these effects result from an increase taking place in the solubility of the hydrated alumina siliceous substances present at the particle surface of the hydraulic substance due to the fact that the 3,6-endomethylene-hexahydro-o-phthalic acid-4-sulfonic acid derivatives are highly soluble in water, with the consequence that the hydration reaction is promoted.

The following examples are given for specifically illustrating the present invention.

EXAMPLE 1 Eight parts by weight of sodium hydroxide and 16.4 parts by weight of 3,6-endomethylene-l,2,3,6-tetrahydrophthalic anhydride were added to 100 parts by weight of water to obtain a homogeneous solution of disodium-3,-endomethylene-l ,2,3,6-tetrahydro-ophthalate. On addition of 10.4 parts by weight of sodium hydrogen sulfite to the so obtained solution and stirring the mixture, the reaction proceeded exothermically. After the evolution of heat has stopped, the stirring was continued for a further 2 hours at C. The water was then removed with the use of a rotating evaporator to obtain 33 parts by weight of a white powder of trisodium-3,dendomethylene-hexahydro-o-phthalic acid4-sulfonate [l].

A concrete test was conducted for clarifying the performance of this compound [I] when used as a concrete additive. The results obtained are shown in Table l.

The composition of the concrete used in the test was as follows:

Portland cement 300 kg/m Coarse aggregates 1200 kg/m (river gravel of maximum particle diameter of 25 mm Fine aggregates 760 kg/m (river gravel of maximum particle (ratio of fine diameter of 2.5 mm) aggregates 39%) However, in the case of the control experiment not using the additive, the amount of fine aggregates was changed to 800 kg/cm (fine aggregates 40 percent).

Table l Additive Compressive Ratio of Water to strength addition cement Slump Amount (kg/cm) Name to ratio (cm) of air cement After After 7 days 28 days 4. Present Compound 0.125 45 55.5 2.2 230 359 nfi: .10 Ira '71) '2! T bl 1 -(onlinucd Additive Compressive Ratio of Water to strength addition cement Slump Amount (kg/cm) Name to ratio (cm) of air cement After After 7 days 28 days Not added 53 6.5 1.6 181 291 Commercial Control lignin sulfonic 0.25 45 6.5 4.1 224 335 acid type additive Note: The slump. amount of air and compressive strength were determined in accordance with the JlSA Methods 1 101.

l 116 and l 108. respectively.

Table 2 Additive Compressive Ratio of Water to Slump Amount strength addition cement (cm) of air (kg/cm) Name to ratio (56) cement (56) After After 7 days 28 days Present Com und inven- ("g 0.25 45 7.1 3.0 224 356 tion Com und Control not added 53 6.5 1.5 220 337 It is apparent from the table that the performances of the concrete incorporated with the compound [1] of the present invention are much superior to the performances of the concrete incorporated with the commercial ligninsulfonic acid type additive not to mention the concrete not incorporated with an additive.

EXAMPLE 2 By operating as in Example 1 but using 17.8 parts by weight of 5-methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride instead of 16.4 parts by weight of 3,6-endomethylene-l,2,3,6-tetrahydrophthalic anhydride, 34.4 parts by weight of trisodium-S- methyl-3,6-endomethy1enehexahydro-o-phthalic acid- 4-sulfonate [11] was obtained.

Operating in like manner but using 20.8 parts by weight of 5-carboxy-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride instead of 16.4 parts by weight of 3,6-endomethylene-l,2,3,6-tetrahydrophthalic anhydride and by using the sodium hydroxide in an amount of 12 parts by weight, 37.4 parts by weight of tetrasodium-5-carboxy-3,6-endomethylene-hexahydro-o-phthalic acid-4-sulfonate [Ill] was obtained.

For clarifying the performances of the compounds [11] and [111], when used as a concrete additive, a concrete test was conducted, with the results shown in Table. The composition of the concretes used in the test was the same as that of Example 1.

It can be appreciated from Table 2 that, despite the fact that the amount used of water is less in the case of the concrete incorporated with the invention compounds [II] and [[11] than in the case of the concrete not incorporated with an additive, satisfactory fluidity is demonstrated. In addition, it is seen that the strength enhancement effect of the concrete incorporated with the invention compounds is greater after the concrete has set.

I claim:

1. A hydraulic composition comprising parts by weight of a hydraulic substance and 0.01 5 parts by weight of a 3,6-endomethylene-hexahydro-o-phthalic acid-4-sulfonic acid derivative of the formula COCM wherein R is a member selected from the group consisting of hydrogen. an alkyl radical of 1 4 carbon atoms and the -COOM group, and M is a member selected from the group consisting of hydrogen, an alkali metal atom, a half atom of an alkaline earth metal and the ammonium group, which M may be the same or different.

2. A composition according to claim 1 wherein the hydraulic substance is portland cement.

UNITED STATES PATENT OFFICE 4 /d4 f CERTIFICATE OF CORRECTION PATENT NO. 3,870,533 g DATED March 11, 1975 INVENTOR(S) SHUNICHIRO OGURA It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading, correct patentee's Foreign Application Priority Data to read as follows:

-- Dec. 8, 1.972 Japan 47-123103 Signed and sealed this 29th day of April 1975.

(SEAL) Attest: C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,870,533

DATED March 11, 1975 |NVENTOR(5) I SHUNICHIRO OGURA It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading, correct patentee' s Foreign Application Priority Data to read 'as follows:

-- Dec. 8, 1972 Japan 47-123103 Signed and sealed this 29th day of April 1975.

(SEAL) test: 0. MARSHALL DANN RUTH C. MASON Commissioner of Patents Atte sting Officer and Trademarks 

1. A HYDRAULIC COMPOSITION COMPRISING 100 PARTS BY WEIGHT OF A HYDRAULIC SUBSTANCE AND 0.01-5 PARTS BY WEIGHT OF A 3.6-ENDOMETHYLENE:HEXAHYDRO-O-PHTHALIC ACID-4-SULFONIC ACID DERIVATIVE OF THE FORMULA
 1. A hydraulic composition comprising 100 parts by weight of a hydraulic substance and 0.01 - 5 parts by weight of a 3,6-endomethylene-hexahydro-o-phthalic acid-4-sulfonic acid derivative of the formula 